In-situ supported non-metallocene catalyst on magnesium support, its preparation method and application

Abstract

The present application relates to a kind of magnesium carrier in-situ supported non-metallocene catalyst, its preparation method and application.The preparation method of the magnesium carrier in-situ supported non-metallocene catalyst includes the following steps: magnesium compound is dissolved in alcohol, then diluent solvent is added, after mixing, dry, obtain the step of magnesium carrier, wherein the content of alcohol in magnesium carrier is 1.0-3.0wt%, preferably 1.2-2.5wt%, more preferably 1.5-2.0wt% relative to the weight of magnesium carrier;Alkyl aluminum is added to magnesium carrier and reacted, and the magnesium-aluminum carrier is obtained by filtration;In-40~10 ℃, preferably-20~0 ℃, the magnesium-aluminum carrier is treated with non-metallocene ligand and chemical treatment agent selected from group IVB metal compound, to obtain the step of the magnesium carrier in-situ supported non-metallocene catalyst.The supported non-metallocene catalyst has the characteristics of simple and easy preparation method and flexible polymerization activity.

Description

TECHNICAL FIELD

[0001] The present application relates to a magnesium carrier in-situ supported non-metallocene catalyst, its preparation method and application. Specifically, the present application relates to a method for in-situ supporting non-metallocene catalyst on a magnesium compound carrier to obtain a supported non-metallocene catalyst, and its application in olefin homopolymerization / copolymerization. BACKGROUND

[0002] Non-metallocene catalysts do not contain cyclopentadienyl groups, and the coordination atoms are oxygen, nitrogen, sulfur and phosphorus. The characteristic is that the central ion has strong electrophilicity, and has a cis-alkyl or halogen metal center structure, which is easy to carry out olefin insertion and σ-bond transfer, and the central metal is easy to be alkylated, which is conducive to the generation of cationic active center; the formed complex has a defined geometric configuration, and the stereoselectivity, electronegativity and chirality can be adjusted. In addition, the metal-carbon bond formed is easy to polarize, which is conducive to the polymerization of olefins. Therefore, even at a relatively high polymerization reaction temperature, a high molecular weight olefin polymer can be obtained.

[0003] However, the homogeneous olefin polymerization catalyst has been proved to have the disadvantages of short activity duration, easy to stick to the kettle, high methylaluminoxane consumption, and too low or too high molecular weight of the obtained polymer, which seriously limits its industrial application.

[0004] The olefin homopolymerization / copolymerization catalyst or catalyst system prepared in patents ZL01126323.7, ZL02151294.9 and ZL02110844.7 has a wide range of olefin homopolymerization / copolymerization performance and is suitable for various forms of polymerization processes. However, a higher amount of cocatalyst is required for the catalyst or catalyst system disclosed in the patents to obtain suitable olefin polymerization activity, and there is a phenomenon of sticking to the kettle during polymerization.

[0005] The common practice is to prepare a supported catalyst by certain loading technology of non-metallocene catalyst, so as to improve the polymerization performance of olefins and the particle morphology of the obtained polymer. It is shown that the initial activity of the catalyst is appropriately reduced to a certain extent, the polymerization activity life of the catalyst is prolonged, the caking or violent polymerization phenomenon during polymerization is reduced or even avoided, the morphology of the polymer is improved, and the apparent density of the polymer is increased, so that it can meet more polymerization processes, such as gas phase polymerization or slurry polymerization, etc.

[0006] For the non-metallocene catalysts disclosed in patents ZL01126323.7, ZL02151294.9, ZL02110844.7 and WO03 / 010207, patents CN1539855A, CN1539856A, CN1789291A, CN1789292A, CN1789290A, WO / 2006 / 063501, CN200510119401.X, etc. adopt various ways to load to obtain supported non-metallocene catalysts, but these patents all involve loading non-metallocene organic compounds containing transition metals (or called non-metallocene catalysts, or non-metallocene complexes) on the treated carrier, either the loading amount of non-metallocene catalysts is low, or the combination of non-metallocene catalysts with the carrier is not very tight.

[0007] Although the silica gel carrier or the composite carrier containing silica gel is used as the carrier of the non-metallocene catalyst, the polymer with good particle morphology can be obtained by polymerization, and the particle size distribution of the polymer can be controlled, but the polymerization activity of the catalyst is low, and since the silica gel is contained in the ash, the application range of the polymer is limited.

[0008] Chinese patent CN200910210990.0 discloses a preparation method of a supported non-metallocene catalyst, comprising the following steps: a step of dissolving a magnesium compound and a non-metallocene ligand in a solvent in the presence of an alcohol to obtain a magnesium compound solution; a step of adding a precipitating agent to the magnesium compound solution to obtain a modified carrier; and a step of treating the modified carrier with a chemical treatment agent selected from a group IVB metal compound to obtain the supported non-metallocene catalyst. According to the disclosure, the introduced alcohol only acts as a cosolvent for the magnesium compound and the non-metallocene ligand, and is then removed by drying during the drying process.

[0009] Chinese patent CN201710814591.X discloses a preparation method of a supported non-metallocene catalyst, comprising the following steps: a step of dissolving a magnesium compound in a solvent in the presence of an alcohol to obtain a magnesium compound solution; a step of drying the magnesium compound solution, or adding a precipitating agent to the magnesium compound solution to obtain a magnesium carrier, wherein the content of the alcohol in the magnesium carrier is 3.0-5.0 wt%, preferably 3.5-4.5 wt%; a step of treating the magnesium carrier with a non-metallocene ligand to obtain a modified carrier; and a step of treating the modified carrier with a chemical treatment agent selected from a group IVB metal compound to obtain the supported non-metallocene catalyst. It adopts two-step treatment of the non-metallocene ligand and the chemical treatment agent, and the preparation process is relatively complex.

[0010] The problem of the supported non-metallocene catalysts in the prior art is that the olefin polymerization activity is low, and in order to improve the activity, a high amount of cocatalyst is necessary. Moreover, the prior art uses silica gel or the like as a support carrier, and thus the polymers obtained by polymerization have a high ash content, which limits the practical use of the polymers. The catalysts supported by magnesium compounds also limit the substantial improvement of the catalyst activity due to the heterogeneous composition and distribution formed during the preparation process.

[0011] Therefore, the current situation is that there is still a need for a supported non-metallocene catalyst which has a simple preparation method, is suitable for industrial production, and can overcome the problems of the supported non-metallocene catalysts in the prior art. SUMMARY

[0012] The present inventors have found, based on the prior art, through catalyst preparation research, polymerization tests and performance analysis, that the use of the supported non-metallocene catalyst prepared by the preparation method of the present application can well solve the aforementioned problems, thereby completing the present application.

[0013] In the preparation method of the supported non-metallocene catalyst of the present application, no proton donor (such as those conventionally used in the art) is added. In addition, in the preparation method of the supported non-metallocene catalyst of the present application, no electron donor (such as the single ester, double ester, diether, diketone and diol ester compounds conventionally used for this purpose in the art) is added, and no ether solvent such as tetrahydrofuran is used in the preparation process. Furthermore, in the preparation method of the supported non-metallocene catalyst of the present application, no harsh reaction requirements and reaction conditions are necessary. Therefore, the preparation method of the supported catalyst is simple and is very suitable for industrial production.

[0014] Specifically, the present application relates to a preparation method of a magnesium carrier in-situ supported non-metallocene catalyst, comprising the following steps:

[0015] dissolving the magnesium compound in alcohol, adding a dilution solvent, mixing and drying to obtain a magnesium carrier, wherein the content of alcohol in the magnesium carrier is 1.0-3.0 wt%, preferably 1.2-2.5 wt%, more preferably 1.5-2.0 wt% relative to the weight of the magnesium carrier; adding alkyl aluminum to the magnesium carrier for reaction, and filtering to obtain a magnesium aluminum carrier; treating the magnesium aluminum carrier with a non-metallocene ligand and a chemical treatment agent selected from a group IVB metal compound at -40-10°C, preferably -20-0°C, to obtain a magnesium carrier in-situ supported non-metallocene catalyst.

[0016] The present application also relates to the magnesium carrier in-situ supported non-metallocene catalyst prepared by the preparation method, and the use thereof in the homopolymerization / copolymerization of olefins.

[0017] Technical effects

[0018] The in-situ preparation method of the magnesium carrier in-situ supported non-metallocene catalyst is simple and feasible, the non-metallocene ligand is uniformly distributed in the magnesium carrier, and the loading amount of the non-metallocene ligand can be adjusted.

[0019] The magnesium carrier in-situ supported non-metallocene catalyst prepared by the method has a significant copolymerization effect, that is, the copolymerization activity of the catalyst is higher than the homopolymerization activity, and the copolymerization reaction can improve the bulk density of the polymer, that is, improve the particle morphology of the polymer.

[0020] Under the homopolymerization reaction condition without hydrogen, the magnesium carrier in-situ supported non-metallocene catalyst provided by the method can be used to polymerize to obtain ultrahigh molecular weight polyethylene with high molecular weight.

[0021] In addition, the magnesium carrier in-situ supported non-metallocene catalyst provided by the method is used to polymerize to obtain a polymer with fine average particle size, uniform distribution and low fine powder content. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 is a graph of the particle size distribution of the polymer of Example Part Table 2 No. 1.

[0023] Figure 2 is a graph of the particle size distribution of the polymer of Example Part Table 2 No. 4. DETAILED DESCRIPTION

[0024] The specific embodiments of the present application will be described in detail below, but it should be pointed out that the protection scope of the present application is not limited by these specific embodiments, but is determined by the claims in the appendix.

[0025] In the context of the present application, unless otherwise specifically defined, or the meaning is beyond the understanding of those skilled in the art, a hydrocarbon or hydrocarbon derivative group of 3 carbon atoms or more (such as propyl, propoxy, butyl, butane, butene, butenyl, hexane, etc.) has the same meaning as when the word "n" is added. For example, propyl is generally understood as n-propyl, and butyl is generally understood as n-butyl.

[0026] In the context of the present application, unless otherwise specifically stated, the physical property value (such as boiling point) of a substance is measured at normal temperature (25°C) and normal pressure (101325 Pa).

[0027] The steps for obtaining the magnesium carrier are described in detail as follows.

[0028] The method for preparing the magnesium support in-situ supported non-metallocene catalyst according to the present application comprises the following steps: dissolving a magnesium compound in an alcohol, adding a dilution solvent, mixing and drying, thereby obtaining the magnesium support. The content of the alcohol in the magnesium support is 1.0-3.0 wt%, preferably 1.2-2.5 wt%, and more preferably 1.5-2.0 wt% relative to the weight of the magnesium support.

[0029] According to the present application, the term "magnesium compound" refers to an organic or inorganic solid anhydrous magnesium-containing compound conventionally used as a support for supported olefin polymerization catalysts, using the general concept in the art.

[0030] According to the present application, as the magnesium compound, for example, magnesium halides, alkoxy magnesium halides, alkoxymagnesiums, alkylmagnesiums, alkyl magnesium halides and alkyl alkoxymagnesiums can be mentioned.

[0031] Specifically, as the magnesium halide, for example, magnesium chloride (MgCl2), magnesium bromide (MgBr2), magnesium iodide (MgI2) and magnesium fluoride (MgF2) and the like can be mentioned, with magnesium chloride being preferred.

[0032] As the alkoxy magnesium halide, for example, methoxy magnesium chloride (Mg(OCH3)Cl), ethoxy magnesium chloride (Mg(OC2H5)Cl), propoxy magnesium chloride (Mg(OC3H7)Cl), n-butoxy magnesium chloride (Mg(OC4H9)Cl), isobutoxy magnesium chloride (Mg(i-OC4H9)Cl), methoxy magnesium bromide (Mg(OCH3)Br), ethoxy magnesium bromide (Mg(OC2H5)Br), propoxy magnesium bromide (Mg(OC3H7)Br), n-butoxy magnesium bromide (Mg(OC4H9)Br), isobutoxy magnesium bromide (Mg(i-OC4H9)Br), methoxy magnesium iodide (Mg(OCH3)I), ethoxy magnesium iodide (Mg(OC2H5)I), propoxy magnesium iodide (Mg(OC3H7)I), n-butoxy magnesium iodide (Mg(OC4H9)I) and isobutoxy magnesium iodide (Mg(i-OC4H9)I) and the like can be mentioned, with methoxy magnesium chloride, ethoxy magnesium chloride and isobutoxy magnesium chloride being preferred.

[0033] As the alkoxymagnesium, for example, methoxy magnesium (Mg(OCH3)2), ethoxy magnesium (Mg(OC2H5)2), propoxy magnesium (Mg(OC3H7)2), butoxy magnesium (Mg(OC4H9)2), isobutoxy magnesium (Mg(i-OC4H9)2) and 2-ethylhexyloxy magnesium (Mg(OCH2CH(C2H5)C4H8)2) and the like can be mentioned, with ethoxy magnesium and isobutoxy magnesium being preferred.

[0034] As the alkyl magnesium, for example, methyl magnesium (Mg(CH3)2), ethyl magnesium (Mg(C2H5)2), propyl magnesium (Mg(C3H7)2), n-butyl magnesium (Mg(C4H9)2), and isobutyl magnesium (Mg(i-C4H9)2), and the like can be given, of which ethyl magnesium and n-butyl magnesium are preferred.

[0035] As the alkyl magnesium halide, for example, methyl magnesium chloride (Mg(CH3)Cl), ethyl magnesium chloride (Mg(C2H5)Cl), propyl magnesium chloride (Mg(C3H7)Cl), n-butyl magnesium chloride (Mg(C4H9)Cl), isobutyl magnesium chloride (Mg(i-C4H9)Cl), methyl magnesium bromide (Mg(CH3)Br), ethyl magnesium bromide (Mg(C2H5)Br), propyl magnesium bromide (Mg(C3H7)Br), n-butyl magnesium bromide (Mg(C4H9)Br), isobutyl magnesium bromide (Mg(i-C4H9)Br), methyl magnesium iodide (Mg(CH3)I), ethyl magnesium iodide (Mg(C2H5)I), propyl magnesium iodide (Mg(C3H7)I), n-butyl magnesium iodide (Mg(C4H9)I), and isobutyl magnesium iodide (Mg(i-C4H9)I), and the like can be given, of which methyl magnesium chloride, ethyl magnesium chloride, and isobutyl magnesium chloride are preferred.

[0036] As the alkyl magnesium alkoxide, there can be mentioned, for example, methyl methylmagnesium (Mg(OCH3)(CH3)), methyl ethylmagnesium (Mg(OC2H5)(CH3)), methyl propylmagnesium (Mg(OC3H7)(CH3)), methyl n-butylmagnesium (Mg(OC4H9)(CH3)), methyl i-butylmagnesium (Mg(i-OC4H9)(CH3)), ethyl methylmagnesium (Mg(OCH3)(C2H5)), ethyl ethylmagnesium (Mg(OC2H5)(C2H5)), ethyl propylmagnesium (Mg(OC3H7)(C2H5)), ethyl n-butylmagnesium (Mg(OC4H9)(C2H5)), ethyl i-butylmagnesium (Mg(i-OC4H9)(C2H5)), propyl methylmagnesium (Mg(OCH3)(C3H7)), propyl ethylmagnesium (Mg(OC2H5)(C3H7)), propyl propylmagnesium (Mg(OC3H7)(C3H7)), propyl n-butylmagnesium (Mg(OC4H9)(C3H7)), propyl i-butylmagnesium (Mg(i-OC4H9)(C3H7)), n-butyl methylmagnesium (Mg(OCH3)(C4H9)), n-butyl ethylmagnesium (Mg(OC2H5)(C4H9)), n-butyl propylmagnesium (Mg(OC3H7)(C4H9)), n-butyl n-butylmagnesium (Mg(OC4H9)(C4H9)), n-butyl i-butylmagnesium (Mg(i-OC4H9)(C4H9)), i-butyl methylmagnesium (Mg(OCH3)(i-C4H9)), i-butyl ethylmagnesium (Mg(OC2H5)(i-C4H9)), i-butyl propylmagnesium (Mg(OC3H7)(i-C4H9)), i-butyl n-butylmagnesium (Mg(OC4H9)(i-C4H9)), and i-butyl i-butylmagnesium (Mg(i-OC4H9)(i-C4H9)), and the like, of which butyl ethylmagnesium is preferred.

[0037] These magnesium compounds can be used singly or in a mixture of two or more, and there is no particular limitation.

[0038] In the case of using a mixture of two or more, the molar ratio between any two of the magnesium compounds in the mixture can be any ratio, for example, 0.25 to 4:1, preferably 0.5 to 3:1, and more preferably 1 to 2:1.

[0039] According to the present application, the term "alcohol" means a compound obtained by replacing at least one hydrogen atom on a hydrocarbon chain (such as C 1-30 hydrocarbon) with a hydroxyl group. It can be one or more selected from the group consisting of aliphatic alcohol, aromatic alcohol, and alicyclic alcohol.

[0040] As the alcohol, there can be mentioned, for example, C 1-30 aliphatic alcohol (preferably C1-30 aliphatic monohydric alcohol), C 6-30 aromatic alcohol (preferably C 6-30 aromatic monohydric alcohol), and C 4-30 alicyclic alcohol (preferably C 4-30 alicyclic monohydric alcohol), wherein preferably C 1-30 aliphatic monohydric alcohol or C 2-8 aliphatic monohydric alcohol, more preferably ethanol and butanol. In addition, the alcohol can be optionally substituted with a substituent selected from a halogen atom or C 1-6 alkoxy group.

[0041] as the C 1-30 aliphatic alcohol, such as methanol, ethanol, propanol, 2-propanol, butanol, pentanol, 2-methylpentanol, 2-ethylpentanol, 2-hexylbutanol, hexanol, and 2-ethylhexanol, etc., wherein ethanol, propanol, butanol, and 2-ethylhexanol are preferred.

[0042] as the C 6-30 aromatic alcohol, such as benzyl alcohol, phenethyl alcohol, and methylbenzyl alcohol, etc., wherein phenethyl alcohol is preferred.

[0043] as the C 4-30 alicyclic alcohol, such as cyclohexanol, cyclopentanol, cyclooctanol, methylcyclopentanol, ethylcyclopentanol, propylcyclopentanol, methylcyclohexanol, ethylcyclohexanol, propylcyclohexanol, methylcyclooctanol, ethylcyclooctanol, and propylcyclooctanol, etc., wherein cyclohexanol and methylcyclohexanol are preferred.

[0044] as the alcohol substituted with a halogen atom, such as trichloromethanol, trichloroethanol, and trichlorohexanol, etc., wherein trichloromethanol is preferred.

[0045] as the alcohol substituted with an alkoxy group, such as ethylene glycol-ethyl ether, ethylene glycol-n-butyl ether, and 1-butoxy-2-propanol, etc., wherein ethylene glycol-ethyl ether is preferred.

[0046] These alcohols can be used singly or in a mixture of a plurality of kinds. In the case of using in a mixture of a plurality of kinds, the ratio between any two of the alcohols in the alcohol mixture can be arbitrarily determined and is not particularly limited.

[0047] According to the present application, the alcohol is preferably one or more selected from aliphatic alcohols, more preferably one or more selected from ethanol, propanol, and butanol.

[0048] According to the present application, as the dilution solvent, one or more selected from alkanes or aromatic hydrocarbons is used. Among them, the alkanes are selected from paraffins, cycloparaffins, halogenated paraffins, and halogenated cycloparaffins.

[0049] As the paraffin, for example, pentane, hexane, heptane, octane, nonane, decane and the like can be given, of which hexane, heptane and decane are preferred, and hexane and decane are most preferred.

[0050] As the cycloparaffin, for example, cyclohexane, cyclopentane, cycloheptane, cyclodecane, cyclononane and the like can be given, of which cyclohexane is most preferred.

[0051] As the halogenated paraffin, for example, dichloromethane, dichlorohexane, dichloroheptane, trichloromethane, trichloroethane, trichlorobutane, dibromomethane, dibromoethane, dibromoheptane, tribromomethane, tribromoethane and tribromobutane and the like can be given.

[0052] As the halogenated cycloparaffin, for example, chlorocyclopentane, chlorocyclohexane, chlorocycloheptane, chlorocyclooctane, chlorocyclononane, chlorocyclodecane, bromocyclopentane, bromocyclohexane, bromocycloheptane, bromocyclooctane, bromocyclononane, bromocyclodecane and the like can be given.

[0053] As the aromatic hydrocarbon, one or more selected from the group consisting of C 6-12 one or more aromatic hydrocarbons, preferably selected from the group consisting of C 6-12 one or more aromatic hydrocarbons, preferably selected from the group consisting of C 6-12 one or more aromatic hydrocarbons, preferably selected from the group consisting of C

[0054] These dilution solvents can be used singly or in a mixture of two or more in any ratio.

[0055] In the preparation of the magnesium carrier, the molar ratio of the magnesium compound to the alcohol, in terms of the element Mg, is 1 : 10 to 50, preferably 1 : 15 to 30. The amount of the dilution solvent used is generally 0.5 to 4 L per 1 mol of the magnesium compound, preferably 1 to 3 L.

[0056] The magnesium compound is dissolved in the alcohol, generally under stirring to facilitate the dissolution. The stirring can be performed in any form, such as a stirring paddle (at a rotation speed of generally 10 to 1000 rpm) and the like. If necessary, the dissolution can be facilitated by appropriate heating, such as at a temperature of 40°C or lower by 5°C than the boiling point of the alcohol.

[0057] In one embodiment of the present application, the magnesium compound is completely dissolved in the alcohol.

[0058] In one embodiment of the present application, the dilution solvent is added to the alcohol solution of the magnesium compound, and after mixing to form a homogeneous solution, the solution is dried to obtain the magnesium carrier.

[0059] The dilution solvent can be added in one portion or dropwise, preferably in one portion. As one of the mixing methods, stirring can be used to facilitate the dispersion of the dilution solvent in the solution, and the stirring can be performed in any form, such as a stirring paddle (at a rotation speed of generally 10 to 1000 rpm) or the like.

[0060] The temperature of the dilution solvent is not particularly limited, and the temperature of the solution can be generally selected to be the temperature at which the magnesium compound is dissolved in the alcohol.

[0061] After the addition of the dilution solvent, the obtained solution of the magnesium compound is dried to remove part of the alcohol therefrom, thereby obtaining the magnesium carrier.

[0062] According to the present application, the drying of the solution of the magnesium compound is performed so that the content of the alcohol in the magnesium carrier is 1.0 to 3.0% by weight, preferably 1.2 to 2.5% by weight, and more preferably 1.5 to 2.0% by weight, relative to the weight of the magnesium carrier.

[0063] According to the present application, the drying can be performed by a conventional method, such as an inert gas drying method, a vacuum drying method, or a heating drying method under vacuum, preferably an inert gas drying method or a heating drying method under vacuum, and most preferably a heating drying method under vacuum.

[0064] According to the present application, the drying method (including the drying temperature, the vacuum degree, and the drying time) is not particularly limited, as long as the content of the alcohol in the magnesium carrier satisfies the aforementioned requirements of the present application. For example, the solution of the magnesium compound is dried at a temperature of 5 to 50°C lower than the boiling point of the dilution solvent, preferably at a temperature of 10 to 30°C lower than the boiling point of the dilution solvent, under a vacuum at an absolute pressure of 2 to 100 mBar, preferably under a vacuum at an absolute pressure of 5 to 50 mBar, for 2 to 30 h, preferably for 4 to 12 h, thereby obtaining the magnesium carrier.

[0065] The steps for obtaining the magnesium-aluminum carrier are described in detail below.

[0066] The method for producing the in-situ supported non-metallocene catalyst of the magnesium carrier of the present application includes the steps of adding an alkyl aluminum to the magnesium carrier to perform a reaction, and filtering to obtain a magnesium-aluminum carrier.

[0067] According to the present application, as the alkyl aluminum, there can be mentioned, for example, a compound represented by the following general formula (I):

[0068] Al(R)3 (I)

[0069] wherein the groups R are the same as or different from each other (preferably the same), and each is independently selected from the group consisting of C1-C8 alkyl groups, preferably methyl, ethyl, and isobutyl, and most preferably methyl.

[0070] Specifically, as the alkylaluminum, there can be mentioned, for example, trimethylaluminum (Al(CH3)3), triethylaluminum (Al(CH3CH2)3), tripropylaluminum (Al(C3H7)3), triisobutylaluminum (Al(i-C4H9)3), tri-n-butylaluminum (Al(C4H9)3), triisopentylaluminum (Al(i-C5H 11 )3), tri-n-pentylaluminum (Al(C5H 11 )3), tri-n-hexylaluminum (Al(C6H 13 )3), triisohexylaluminum (Al(i-C6H 13 )3), diethylmethylaluminum (Al(CH3)(CH3CH2)2), and dimethylethylaluminum (Al(CH3CH2)(CH3)2), etc., with trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and tri-n-hexylaluminum being preferred, and triethylaluminum and triisobutylaluminum being most preferred.

[0071] These alkylaluminums can be used singly or in combination of two or more in any ratio.

[0072] According to the present application, the alkylaluminum is added to the magnesium carrier, either in the presence of an alkane solvent or without the need for an alkane solvent, with the addition being preferably carried out in the presence of an alkane solvent. The alkane solvent can be the same as or different from the alkane solvent in the aforementioned diluent solvent.

[0073] Specifically, as the alkane solvent, there can be mentioned, for example, C 5-12 paraffins, C 5-12 cycloparaffins, halogenated C 5-12 paraffins, halogenated C 5-12 cycloparaffins, etc., such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, chloropentane, chlorohexane, chloroheptane, chlorooctane, chlorononane, chlorodecane, chloroundecane, chlorododecane, and chlorocyclohexane, etc., with pentane, hexane, decane, and cyclohexane being preferred, and hexane being most preferred. These solvents can be used singly or in combination of two or more in any ratio.

[0074] In one embodiment of the present application, as the preparation method of the magnesium-aluminum carrier, first, an alkane solvent is optionally added to the magnesium carrier, and then the alkyl aluminum is metered (preferably slowly added dropwise) under stirring to form a reaction mixture. In one embodiment of the present application, in order to avoid excessive reaction and protect the structure of the magnesium carrier, it is generally required to react for a long time, such as 0.5-12h, preferably 2-8h, at room temperature, and then react for a short time, such as 0.25-2h, preferably 0.5-1h, at 60-100°C. In one embodiment of the present application, the reaction progress can also be controlled by gradient temperature incubation, which is generally incubated at room temperature for 0.25-4h, preferably 0.5-2h, then incubated at 40°C for 0.25-2h, preferably 0.5-1h, then incubated at 60°C for 0.25-2h, preferably 0.5-1h, then incubated at 80°C for 0.25-2h, preferably 0.5-1h, wherein the temperature increasing rate is generally 10-60°C / h. Preferably, the reaction progress is controlled by gradient temperature incubation.

[0075] In one embodiment of the present application, the obtained mixed product is filtered, optionally washed (1-6 times, preferably 1-3 times) and optionally dried to obtain the magnesium-aluminum carrier. In one embodiment of the present application, drying can also not be performed. Preferably, drying is not performed. The washing solvent can be selected from the same alkane solvents as described above, or different alkane solvents, preferably decane and hexane, most preferably hexane.

[0076] According to the present application, the alkyl aluminum is used in an amount such that the molar ratio of the magnesium compound to the alkyl aluminum, calculated as Mg element and Al element respectively, is 1:0.5-5, preferably 1:1-3.

[0077] The following describes the steps for obtaining the magnesium carrier in-situ supported non-metallocene catalyst.

[0078] The preparation method of the magnesium carrier in-situ supported non-metallocene catalyst of the present application comprises the following steps: treating the magnesium-aluminum carrier with a non-metallocene ligand and a chemical treatment agent selected from Group IVB metal compounds at -40-10°C, preferably -20-0°C, to obtain the magnesium carrier in-situ supported non-metallocene catalyst.

[0079] According to the present application, by simultaneously treating the magnesium-aluminum carrier with the non-metallocene ligand and the chemical treatment agent, the chemical treatment agent and the non-metallocene ligand can react to generate a non-metallocene complex in-situ on the magnesium-aluminum carrier (in-situ loading reaction), thereby obtaining the in-situ supported non-metallocene catalyst of the present application.

[0080] According to the present application, the term "non-metallocene complex" is a single-site olefin polymerization catalyst which does not contain a cyclopentadienyl ring, a fluorene ring or an indene ring or the like cyclopentadienyl group or its derivative in its structure and which is a metal organic compound capable of showing an olefin polymerization catalytic activity when combined with a cocatalyst (such as those described below) (and thus the non-metallocene complex is sometimes also referred to as a non-metallocene olefin polymerization complex). The compound contains a central metal atom and at least one polydentate ligand (preferably a tridentate ligand or more) which is bound to the central metal atom by a coordinate bond, and the term "non-metallocene ligand" is the aforementioned polydentate ligand.

[0081] According to the present application, the non-metallocene ligand is selected from the group consisting of compounds having the following chemical formula:

[0082]

[0083] According to the present application, the groups A, D and E (coordination groups) in the compound form a coordinate bond by a coordinate reaction with the IVB group metal atom contained in the IVB group metal compound used as a chemical treatment agent in the present application through the coordination atoms (such as N, O, S, Se and P or the like hetero atom) contained therein, thereby forming a complex (i.e. the non-metallocene complex according to the present application) having the IVB group metal atom as a central metal atom M.

[0084] In a more specific embodiment, the non-metallocene ligand is selected from the group consisting of compounds (A) and compounds (B) having the following chemical formula:

[0085]

[0086] In a more specific embodiment, the non-metallocene ligand is selected from the group consisting of compounds (A-1) to (A-4) and compounds (B-1) to (B-4) having the following chemical formula:

[0087]

[0088]

[0089] In all of the above chemical formulae,

[0090] q is 0 or 1;

[0091] d is 0 or 1;

[0092] A is selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, -NR 23 R 24 , -N(O)R 25 R 26 , -PR 28 R 29 , -P(O)R 30 OR 31 , sulfone, sulfoxide or -Se(O)R 39 wherein N, O, S, Se and P are each a coordinating atom;

[0093] B is selected from a nitrogen atom, a nitrogen-containing group, a phosphorus-containing group or a C1-C 30 hydrocarbon group;

[0094] D is selected from a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a phosphorus atom, a nitrogen-containing group, a phosphorus-containing group, a C1-C 30 hydrocarbon group, a sulfone group or a sulfoxide group, wherein N, O, S, Se and P are each a coordinating atom;

[0095] E is selected from a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group or a cyano group (-CN), wherein N, O, S, Se and P are each a coordinating atom;

[0096] F is selected from a nitrogen atom, a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group or a phosphorus-containing group, wherein N, O, S, Se and P are each a coordinating atom;

[0097] G is selected from a C1-C 30 hydrocarbon group, a substituted C1-C 30 hydrocarbon group or an inert functional group;

[0098] Y is selected from a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group or a phosphorus-containing group, wherein N, O, S, Se and P are each a coordinating atom;

[0099] Z is selected from a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group or a cyano group (-CN), such as can be mentioned -NR 23 R 24 , -N(O)R 25 R 26 , -PR 28 R 29 , -P(O)R 30 R 31 , -OR 34 , -SR 35 , -S(O)R 36 , -SeR 38 or -Se(O)R 39 wherein N, O, S, Se and P are each a coordinating atom;

[0100] → represents a single or double bond;

[0101] - represents a covalent or ionic bond.

[0102] R 1 to R 4 , R 6 to R 21 are each independently selected from the group consisting of hydrogen, C1-C 30 alkyl, substituted C1-C 30 alkyl (wherein halogenated alkyl groups such as -CH2Cl and -CH2CH2Cl are preferred) or an inert functional group. R 22 to R 36 , R 38 and R 39 are each independently selected from the group consisting of hydrogen, C1-C 30 alkyl or substituted C1-C 30 alkyl (wherein halogenated alkyl groups such as -CH2Cl and -CH2CH2Cl are preferred). The above groups can be the same as or different from each other, wherein adjacent groups such as R 1 and R 2 , R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 18 and R 19 , R 19 and R 20 , R 20 and R 21 , R 23 and R 24 , or R 25 and R 26 may be bonded together to form a bond or a ring, preferably an aromatic ring, such as an unsubstituted benzene ring or a benzene ring substituted with 1 to 4 C1-C 30 alkyl or substituted C1-C 30 alkyl (wherein halogenated alkyl groups such as -CH2Cl and -CH2CH2Cl are preferred).

[0103] R 5 is selected from the group consisting of a lone pair of electrons on nitrogen, hydrogen, C1-C 30 alkyl, substituted C1-C 30 alkyl, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group or a phosphorus-containing group. When R 5 is an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group or a phosphorus-containing group, R 5N, O, S, P and Se in the above formulae can act as coordinating atoms (coordinating to the central metal atom M).

[0104] In the context of the present application, the inert functional groups can be mentioned, for example, selected from halogen, oxygen-containing groups, nitrogen-containing groups, silicon-containing groups, germanium-containing groups, sulfur-containing groups, tin-containing groups, C1-C 10 C1-C 30 hydrocarbyl groups and substituted C1-C 30 hydrocarbyl groups.

[0105] In the context of the present application, the inert functional groups have the following characteristics, limited by the chemical structure of the multidentate ligand according to the present application:

[0106] (1) do not interfere with the coordination process of the groups A, D, E, F, Y or Z to the central metal atom M, and

[0107] (2) have a lower coordinating ability to the central metal atom M than the A, D, E, F, Y and Z groups, and do not displace the existing coordination of these groups to the central metal atom M.

[0108] According to the present application, in all of the above chemical formulae, any two or more adjacent groups, such as R 21 to group Z, or R 13 to group Y, can be combined together to form a ring, preferably a C6-C 30 aromatic heterocycle, such as a pyridine ring, etc., wherein the aromatic heterocycle is optionally substituted with 1 or more substituents selected from C1-C 30 hydrocarbyl groups and substituted C1-C 30 hydrocarbyl groups.

[0109] In the context of the present application, the halogen is selected from F, Cl, Br or I. The nitrogen-containing group is selected from -NR 23 R 24 , -T-NR 23 R 24 or -N(O)R 25 R 26 . The phosphorus-containing group is selected from -PR 28 R 29 , -P(O)R 30 R 31 or -P(O)R 32 (OR 33 ). The oxygen-containing group is selected from hydroxyl, -OR 34 and -T-OR34 The sulfur-containing group is selected from -SR. 35 -T-SR 35 -S(O)R 36 or -T-SO2R 37 The selenium-containing group is selected from -SeR. 38 -T-SeR 38 -Se(O)R 39 or-T-Se(O)R 39 The group T is selected from C1-C1. 30 Hydrocarbon group or substituted C1-C 30 Hydrocarbon group. The R... 37 Selected from hydrogen, C1-C 30 Hydrocarbon group or substituted C1-C 30 Hydrocarbon group.

[0110] In the context of this invention, the C1-C 30 Hydrocarbon groups are selected from C1-C 30 Alkyl (preferably C1-C6 alkyl, such as isobutyl), C7-C 30 Alkyl aryl (such as tolyl, xylyl, diisobutylphenyl, etc.), C7-C 30 Aryl groups (e.g., benzyl), C3-C 30 Cycloalkyl, C2-C 30 alkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl (e.g., phenyl, naphthyl, anthracene, etc.), C8-C 30 Fused ring groups or C4-C 30 Heterocyclic groups, wherein the heterocyclic group contains 1-3 heteroatoms selected from nitrogen, oxygen or sulfur atoms, such as pyridyl, pyrrole, furanyl or thiophene.

[0111] According to the present invention, in the context of the present invention, depending on the specific circumstances of the associated groups to which they are attached, the C1-C 30 Hydrocarbon groups sometimes refer to C1-C 30 Hydrocarbon dimethyl (divalent group, or C1-C) 30 (hydro-ion group) or C1-C 30 The trivalent hydrocarbon group is obvious to those skilled in the art.

[0112] In the context of this invention, the substituted C1-C 30 Hydrocarbon group refers to a C1-C group with one or more inert substituents. 30 Hydrocarbon group. Inert substituents refer to substituents that coordinate with the aforementioned coordination groups (referring to groups A, D, E, F, Y, and Z, or optionally including R). 5The coordination process between the substituents and the central metal atom M (i.e., the aforementioned group IVB metal atom) is not substantially interfered with; in other words, due to the chemical structure of the ligands of this invention, these substituents are unable or have no opportunity (e.g., due to steric hindrance) to undergo a coordination reaction with the group IVB metal atom to form a coordinate bond. Generally, the inert substituents are selected from halogens or C1-C... 30 Alkyl group (preferably C1-C6 alkyl group, such as isobutyl group).

[0113] In the context of this invention, the silicon-containing group is selected from -SiR 42 R 43 R 44 or -T-SiR 45 The germanium-containing group is selected from -GeR. 46 R 47 R 48 or -T-GeR 49 The tin-containing group is selected from -SnR. 50 R 51 R 52 -T-SnR 53 or -T-Sn(O)R 54 ; and the R 42 To R 54 Each is independently selected from hydrogen, the aforementioned C1-C 30 Hydrocarbon group or the aforementioned substituted C1-C 30 Hydrocarbon groups, which may be the same or different from each other, and adjacent groups may be bonded together to form bonds or rings. The definition of group T is the same as before.

[0114] Examples of non-metallocene ligands include the following compounds:

[0115]

[0116]

[0117]

[0118]

[0119] The non-metallocene ligand is preferably selected from the following compounds:

[0120]

[0121]

[0122] The non-metallocene ligand is further preferably selected from the following compounds:

[0123]

[0124] The non-metallocene ligand is more preferably selected from the following compounds:

[0125]

[0126] These non-metallocene ligands can be used singly or in combination in any ratio.

[0127] According to the present application, the non-metallocene ligand is not a diether compound which is commonly used as an electron donor compound in the art.

[0128] The non-metallocene ligand can be manufactured by any method known to those skilled in the art. For details of the manufacturing method thereof, reference can be made to, for example, WO 03 / 010207 and Chinese Patents ZL01126323.7 and ZL02110844.7, etc., the entire contents of which are incorporated herein by reference.

[0129] The chemical treatment agent will be described in detail below.

[0130] According to the present application, a Group IVB metal compound is used as the chemical treatment agent.

[0131] As the Group IVB metal compound, there can be mentioned, for example, a Group IVB metal halide, a Group IVB metal alkyl compound, a Group IVB metal alkoxide compound, a Group IVB metal alkyl halide and a Group IVB metal alkoxide halide.

[0132] As the Group IVB metal halide, the Group IVB metal alkyl compound, the Group IVB metal alkoxide compound, the Group IVB metal alkyl halide and the Group IVB metal alkoxide halide, there can be mentioned, for example, a compound having the following general formula (II):

[0133] M(OR 1 ) m X n R 2 4-m-n (II)

[0134] In formula (II):

[0135] m is 0, 1, 2, 3 or 4;

[0136] n is 0, 1, 2, 3 or 4;

[0137] M is a Group IVB metal in the Periodic Table of Elements, such as titanium, zirconium and hafnium, etc.;

[0138] X is a halogen, such as F, Cl, Br and I; and

[0139] R1 and R 2 each independently is selected from C 1-10 alkyl, such as methyl, ethyl, propyl, n-butyl, isobutyl, and the like, R 1 and R 2 may be the same or different.

[0140] Specifically, as the Group IV B metal halide, for example, titanium tetrafluoride (TiF4), titanium tetrachloride (TiCl4), titanium tetrabromide (TiBr4), titanium tetraiodide (TiI4) can be mentioned;

[0141] zirconium tetrafluoride (ZrF4), zirconium tetrachloride (ZrCl4), zirconium tetrabromide (ZrBr4), zirconium tetraiodide (ZrI4);

[0142] hafnium tetrafluoride (HfF4), hafnium tetrachloride (HfCl4), hafnium tetrabromide (HfBr4), hafnium tetraiodide (HfI4).

[0143] As the Group IV B metal alkyl compound, for example, titanium tetramethyl (Ti(CH3)4), titanium tetraethyl (Ti(CH3CH2)4), titanium tetraisobutyl (Ti(i-C4H9)4), titanium tetra-n-butyl (Ti(C4H9)4), titanium trimethyl ethyl (Ti(CH3)(CH3CH2)3), titanium diethyl dimethyl (Ti(CH3)2(CH3CH2)2), titanium trimethyl ethyl (Ti(CH3)3(CH3CH2)), titanium triisobutyl methyl (Ti(CH3)(i-C4H9)3), titanium diisobutyl dimethyl (Ti(CH3)2(i-C4H9)2), titanium trimethyl isobutyl (Ti(CH3)3(i-C4H9)), titanium triisobutyl ethyl (Ti(CH3CH2)(i-C4H9)3), titanium diisobutyl diethyl (Ti(CH3CH2)2(i-C4H9)2), titanium triethyl isobutyl (Ti(CH3CH2)3(i-C4H9)), titanium tri-n-butyl methyl (Ti(CH3)(C4H9)3), titanium di-n-butyl dimethyl (Ti(CH3)2(C4H9)2), titanium trimethyl n-butyl (Ti(CH3)3(C4H9)), titanium tri-n-butyl ethyl (Ti(CH3CH2)(C4H9)3), titanium di-n-butyl diethyl (Ti(CH3CH2)2(C4H9)2), titanium triethyl n-butyl (Ti(CH3CH2)3(C4H9)), and the like can be mentioned;

[0144] tetraethylzirconium (Zr(CH3CH2)4), tetraisobutylzirconium (Zr(i-C4H9)4), tetra-n- butylzirconium (Zr(C4H9)4), triethylmethylzirconium (Zr(CH3)(CH3CH2)3), diethyldimethylzirconium (Zr(CH3)2(CH3CH2)2), trimethylethylzirconium (Zr(CH3)3(CH3CH2)), triisobutylmethylzirconium (Zr(CH3)(i-C4H9)3), diisobutyldimethylzirconium (Zr(CH3)2(i-C4H9)2), trimethylisobutylzirconium (Zr(CH3)3(i-C4H9)), triisobutylethylzirconium (Zr(CH3CH2)(i-C4H9)3), diisobutyldiethylzirconium (Zr(CH3CH2)2(i-C4H9)2), triethylisobutylzirconium (Zr(CH3CH2)3(i-C4H9)), tri-n- butylmethylzirconium (Zr(CH3)(C4H9)3), di-n-butyldimethylzirconium (Zr(CH3)2(C4H9)2), trimethyl-n-butyhzirconium (Zr(CH3)3(C4H9)), tri-n-butyiethylzirconium (Zr(CH3CH2)(C4H9)3), di-n-butyldiethylzirconium (Zr(CH3CH2)2(C4H9)2), triethyl-n-butyhzirconium (Zr(CH3CH2)3(C4H9)), and the like;

[0145] tetraethylhafnium (Hf(CH3CH2)4), tetraisobutylhafnium (Hf(i-C4H9)4), tetra-n- butylhafnium (Hf(C4H9)4), triethylmethylhafnium (Hf(CH3)(CH3CH2)3), diethyldimethylhafnium (Hf(CH3)2(CH3CH2)2), trimethylethylhafnium (Hf(CH3)3(CH3CH2)), triisobutylmethylhafnium (Hf(CH3)(i-C4H9)3), diisobutyldimethylhafnium (Hf(CH3)2(i-C4H9)2), trimethylisobutylhafnium (Hf(CH3)3(i-C4H9)), triisobutylethylhafnium (Hf(CH3CH2)(i-C4H9)3), diisobutyldiethylhafnium (Hf(CH3CH2)2(i-C4H9)2), triethylisobutylhafnium (Hf(CH3CH2)3(i-C4H9)), tri-n- butylmethylhafnium (Hf(CH3)(C4H9)3), di-n-butyldimethylhafnium (Hf(CH3)2(C4H9)2), trimethyl-n-butyhzirconium (Hf(CH3)3(C4H9)), tri-n-butyiethylhafnium (Hf(CH3CH2)(C4H9)3), di-n-butyldiethylhafnium (Hf(CH3CH2)2(C4H9)2), triethyl-n-butyhzirconium (Hf(CH3CH2)3(C4H9)), and the like.

[0146] As the Group IVB metal alkoxide compounds, for example, tetramethoxytitanium (Ti(OCH3)4), tetraethoxytitanium (Ti(OCH3CH2)4), tetraisobutyloxytitanium (Ti(i-OC4H9)4), tetra-n-butyloxytitanium (Ti(OC4H9)4), triethoxymethoxytitanium (Ti(OCH3)(OCH3CH2)3), diethoxydimethoxytitanium (Ti(OCH3)2(OCH3CH2)2), trimethoxyethoxytitanium (Ti(OCH3)3(OCH3CH2)), triisobutyloxymethoxytitanium (Ti(OCH3)(i-OC4H9)3), diisobutyloxydimethoxytitanium (Ti(OCH3)2(i-OC4H9)2), trimethoxyisobutyloxytitanium (Ti(OCH3)3(i-OC4H9)), triisobutyloxyethoxytitanium (Ti(OCH3CH2)(i-OC4H9)3), diisobutyloxydiethoxytitanium (Ti(OCH3CH2)2(i-OC4H9)2), triethoxyisobutyloxytitanium (Ti(OCH3CH2)3(i-OC4H9)), tri-n-butyloxymethoxytitanium (Ti(OCH3)(OC4H9)3), di-n-butyloxydimethoxytitanium (Ti(OCH3)2(OC4H9)2), trimethoxy-n-butyloxytitanium (Ti(OCH3)3(OC4H9)), tri-n-butyloxyethoxytitanium (Ti(OCH3CH2)(OC4H9)3), di-n-butyloxydiethoxytitanium (Ti(OCH3CH2)2(OC4H9)2), triethoxy-n-butyloxytitanium (Ti(OCH3CH2)3(OC4H9)), and the like can be given.

[0147] tetraethoxysilane (Si(OCH2CH3)4), tetraisobutoxysilane (Si(i-OC4H9)4), tetra-n-butoxysilane (Si(OC4H9)4), triethoxymethoxysilane (Si(OCH3)(OCH2CH3)3), diethoxydimethoxysilane (Si(OCH3)2(OCH2CH2)2), tri-methoxyethoxysilane (Si(OCH3)3(OCH2CH2)), triisobutoxymethoxysilane (Si(OCH3)(i-OC4H9)3), diisobutoxydimethoxysilane (Si(OCH3)2(i-OC4H9)2), tri-methoxyisobutoxysilane (Si(OCH3)3(i-C4H9)), triisobutoxyethoxysilane (Si(OCH2CH2)(i-OC4H9)3), diisobutoxydiethoxysilane (Si(OCH2CH2)2(i-OC4H9)2), tri-ethoxyisobutoxysilane (Si(OCH2CH2)3(i-OC4H9)), tri-n-butoxymethoxysilane (Si(OCH3)(OC4H9)3), di-n-butoxydimethoxysilane (Si(OCH3)2(OC4H9)2), tri-methoxy-n-butoxysilane (Si(OCH3)3(OC4H9)), tri-n-butoxyethoxysilane (Si(OCH2CH2)(OC4H9)3), di-n-butoxydiethoxysilane (Si(OCH2CH2)2(OC4H9)2), tri-ethoxy-n-butoxysilane (Si(OCH2CH2)3(OC4H9)), and the like;

[0148] tetraethoxyhafnium (Hf(OCH3CH2)4), tetraisobutoxyhafnium (Hf(i-OC4H9)4), tetra-n-butoxyhafnium (Hf(OC4H9)4), triethoxymethoxyhafnium (Hf(OCH3)(OCH3CH2)3), diethoxydimethoxyhafnium (Hf(OCH3)2(OCH3CH2)2), trimethoxyethoxyhafnium (Hf(OCH3)3(OCH3CH2)), triisobutoxymethoxyhafnium (Hf(OCH3)(i-OC4H9)3), diisobutoxydimethoxyhafnium (Hf(OCH3)2(i-OC4H9)2), triisobutoxyethoxyhafnium (Hf(OCH3CH2)(i-OC4H9)3), diisobutoxydiethoxyhafnium (Hf(OCH3CH2)2(i-OC4H9)2), triethoxyisobutoxyhafnium (Hf(OCH3CH2)3(i-C4H9)), tri-n-butoxymethoxyhafnium (Hf(OCH3)(OC4H9)3), di-n-butoxydimethoxyhafnium (Hf(OCH3)2(OC4H9)2), tri-n-butoxyethoxyhafnium (Hf(OCH3)3(OC4H9)), and the like.

[0149] As the Group IV B metal alkyl halide, for example, there can be mentioned titanium trimethyl chloride (TiCl(CH3)3), titanium triethyl chloride (TiCl(CH3CH2)3), titanium triisobutyl chloride (TiCl(i-C4H9)3), titanium tri-n-butyl chloride (TiCl(C4H9)3), titanium dimethyl dichloride (TiCl2(CH3)2), titanium diethyl dichloride (TiCl2(CH3CH2)2), titanium diisobutyl dichloride (TiCl2(i-C4H9)2), titanium tri-n-butyl chloride (TiCl(C4H9)3), titanium methyl trichloride (Ti(CH3)Cl3), titanium ethyl trichloride (Ti(CH3CH2)Cl3), titanium isobutyl trichloride (Ti(i-C4H9)Cl3), titanium n-butyl trichloride (Ti(C4H9)Cl3);

[0150] trimethyl titanium bromide (TiBr(CH3)3), triethyl titanium bromide (TiBr(CH3CH2)3), triisobutyl titanium bromide (TiBr(i-C4H9)3), tri-n-butyl titanium bromide (TiBr(C4H9)3), dimethyl titanium dibromide (TiBr2(CH3)2), diethyl titanium dibromide (TiBr2(CH3CH2)2), diisobutyl titanium dibromide (TiBr2(i-C4H9)2), tri-n-butyl titanium bromide (TiBr(C4H9)3), methyl titanium tribromide (Ti(CH3)Br3), ethyl titanium tribromide (Ti(CH3CH2)Br3), isobutyl titanium tribromide (Ti(i-C4H9)Br3), n-butyl titanium tribromide (Ti(C4H9)Br3);

[0151] trimethyl zirconium chloride (ZrCl(CH3)3), triethyl zirconium chloride (ZrCl(CH3CH2)3), triisobutyl zirconium chloride (ZrCl(i-C4H9)3), tri-n-butyl zirconium chloride (ZrCl(C4H9)3), dimethyl zirconium dichloride (ZrCl2(CH3)2), diethyl zirconium dichloride (ZrCl2(CH3CH2)2), diisobutyl zirconium dichloride (ZrCl2(i-C4H9)2), tri-n-butyl zirconium chloride (ZrCl(C4H9)3), methyl zirconium trichloride (Zr(CH3)Cl3), ethyl zirconium trichloride (Zr(CH3CH2)Cl3), isobutyl zirconium trichloride (Zr(i-C4H9)Cl3), n-butyl zirconium trichloride (Zr(C4H9)Cl3);

[0152] trimethyl zirconium bromide (ZrBr(CH3)3), triethyl zirconium bromide (ZrBr(CH3CH2)3), triisobutyl zirconium bromide (ZrBr(i-C4H9)3), tri-n-butyl zirconium bromide (ZrBr(C4H9)3), dimethyl zirconium dibromide (ZrBr2(CH3)2), diethyl zirconium dibromide (ZrBr2(CH3CH2)2), diisobutyl zirconium dibromide (ZrBr2(i-C4H9)2), tri-n-butyl zirconium bromide (ZrBr(C4H9)3), methyl zirconium tribromide (Zr(CH3)Br3), ethyl zirconium tribromide (Zr(CH3CH2)Br3), isobutyl zirconium tribromide (Zr(i-C4H9)Br3), n-butyl zirconium tribromide (Zr(C4H9)Br3);

[0153] trimethylhafnium chloride (HfCI(CH3)3), triethylhafnium chloride (HfCI(CH3CH2)3), triisobutylhafnium chloride (HfCI(i-C4H9)3), tri-n-butylhafnium chloride (HfCI(C4H9)3), dimethylhafnium dichloride (HfCI2(CH3)2), diethylhafnium dichloride (HfCI2(CH3CH2)2), diisobutylhafnium dichloride (HfCI2(i-C4H9)2), tri-n-butylhafnium chloride (HfCI(C4H9)3), methylhafnium trichloride (Hf(CH3)CI3), ethylhafnium trichloride (Hf(CH3CH2)CI3), isobutylhafnium trichloride (Hf(i-C4H9)CI3), n-butylhafnium trichloride (Hf(C4H9)CI3);

[0154] trimethylhafnium bromide (HfBr(CH3)3), triethylhafnium bromide (HfBr(CH3CH2)3), triisobutylhafnium bromide (HfBr(i-C4H9)3), tri-n-butylhafnium bromide (HfBr(C4H9)3), dimethylhafnium dibromide (HfBr2(CH3)2), diethylhafnium dibromide (HfBr2(CH3CH2)2), diisobutylhafnium dibromide (HfBr2(i-C4H9)2), tri-n-butylhafnium bromide (HfBr(C4H9)3), methylhafnium tribromide (Hf(CH3)Br3), ethylhafnium tribromide (Hf(CH3CH2)Br3), isobutylhafnium tribromide (Hf(i-C4H9)Br3), n-butylhafnium tribromide (Hf(C4H9)Br3).

[0155] As the Group IVB metal alkyl halide, for example, trimethoxytitanium chloride (TiCI(OCH3)3), triethoxytitanium chloride (TiCI(OCH3CH2)3), triisobutoxytitanium chloride (TiCI(i-OC4H9)3), tri-n-butoxytitanium chloride (TiCI(OC4H9)3), dimethoxytitanium dichloride (TiCI2(OCH3)2), diethoxytitanium dichloride (TiCI2(OCH3CH2)2), diisobutoxytitanium dichloride (TiCI2(i-OC4H9)2), tri-n-butoxytitanium chloride (TiCI(OC4H9)3), methoxytitanium trichloride (Ti(OCH3)CI3), ethoxytitanium trichloride (Ti(OCH3CH2)CI3), isobutoxytitanium trichloride (Ti(i-C4H9)CI3), n-butoxytitanium trichloride (Ti(OC4H9)CI3);

[0156] trimethoxy titanium bromide (TiBr(OCH3)3), triethoxy titanium bromide (TiBr(OCH3CH2)3), triisobutoxy titanium bromide (TiBr(i-OC4H9)3), tri-n-butoxy titanium bromide (TiBr(OC4H9)3), dimethoxy titanium dibromide (TiBr2(OCH3)2), diethoxy titanium dibromide (TiBr2(OCH3CH2)2), diisobutoxy titanium dibromide (TiBr2(i-OC4H9)2), tri-n-butoxy titanium bromide (TiBr(OC4H9)3), methoxy titanium tribromide (Ti(OCH3)Br3), ethoxy titanium tribromide (Ti(OCH3CH2)Br3), isobutoxy titanium tribromide (Ti(i-C4H9)Br3), n-butoxy titanium tribromide (Ti(OC4H9)Br3);

[0157] trimethoxy zirconium chloride (ZrCl(OCH3)3), triethoxy zirconium chloride (ZrCl(OCH3CH2)3), triisobutoxy zirconium chloride (ZrCl(i-OC4H9)3), tri-n-butoxy zirconium chloride (ZrCl(OC4H9)3), dimethoxy zirconium dichloride (ZrCl2(OCH3)2), diethoxy zirconium dichloride (ZrCl2(OCH3CH2)2), diisobutoxy zirconium dichloride (ZrCl2(i-OC4H9)2), tri-n-butoxy zirconium chloride (ZrCl(OC4H9)3), methoxy zirconium trichloride (Zr(OCH3)Cl3), ethoxy zirconium trichloride (Zr(OCH3CH2)Cl3), isobutoxy zirconium trichloride (Zr(i-C4H9)Cl3), n-butoxy zirconium trichloride (Zr(OC4H9)Cl3);

[0158] trimethoxy zirconium bromide (ZrBr(OCH3)3), triethoxy zirconium bromide (ZrBr(OCH3CH2)3), triisobutoxy zirconium bromide (ZrBr(i-OC4H9)3), tri-n-butoxy zirconium bromide (ZrBr(OC4H9)3), dimethoxy zirconium dibromide (ZrBr2(OCH3)2), diethoxy zirconium dibromide (ZrBr2(OCH3CH2)2), diisobutoxy zirconium dibromide (ZrBr2(i-OC4H9)2), tri-n-butoxy zirconium bromide (ZrBr(OC4H9)3), methoxy zirconium tribromide (Zr(OCH3)Br3), ethoxy zirconium tribromide (Zr(OCH3CH2)Br3), isobutoxy zirconium tribromide (Zr(i-C4H9)Br3), n-butoxy zirconium tribromide (Zr(OC4H9)Br3);

[0159] trimethoxyhafnium chloride (HfCl(OCH3)3), triethoxyhafnium chloride (HfCl(OCH3CH2)3), triisobutoxyhafnium chloride (HfCl(i-OC4H9)3), tri-n-butoxyhafnium chloride (HfCl(OC4H9)3), dimethoxyhafnium dichloride (HfCl2(OCH3)2), diethoxyhafnium dichloride (HfCl2(OCH3CH2)2), diisobutoxyhafnium dichloride (HfCl2(i-OC4H9)2), tri-n-butoxyhafnium chloride (HfCl(OC4H9)3), methoxyhafnium trichloride (Hf(OCH3)Cl3), ethoxyhafnium trichloride (Hf(OCH3CH2)Cl3), isobutoxyhafnium trichloride (Hf(i-C4H9)Cl3), n-butoxyhafnium trichloride (Hf(OC4H9)Cl3);

[0160] trimethoxyhafnium bromide (HfBr(OCH3)3), triethoxyhafnium bromide (HfBr(OCH3CH2)3), triisobutoxyhafnium bromide (HfBr(i-OC4H9)3), tri-n-butoxyhafnium bromide (HfBr(OC4H9)3), dimethoxyhafnium dibromide (HfBr2(OCH3)2), diethoxyhafnium dibromide (HfBr2(OCH3CH2)2), diisobutoxyhafnium dibromide (HfBr2(i-OC4H9)2), tri-n-butoxyhafnium bromide (HfBr(OC4H9)3), methoxyhafnium tribromide (Hf(OCH3)Br3), ethoxyhafnium tribromide (Hf(OCH3CH2)Br3), isobutoxyhafnium tribromide (Hf(i-C4H9)Br3), n-butoxyhafnium tribromide (Hf(OC4H9)Br3).

[0161] As the Group IVB metal compound, the Group IVB metal halide is preferred, and TiCl4, TiBr4, ZrCl4, ZrBr4, HfCl4and HfBr4are more preferred, and TiCl4and ZrCl4are most preferred.

[0162] These Group IVB metal compounds can be used singly or in combination of a plurality of kinds in any ratio.

[0163] When the chemical treatment agent is liquid at ordinary temperature, the chemical treatment reaction can be carried out directly using the chemical treatment agent. When the chemical treatment agent is solid at ordinary temperature, the chemical treatment agent is preferably used in the form of a solution for the sake of ease of metering and handling. Of course, when the chemical treatment agent is liquid at ordinary temperature, the chemical treatment agent can be used in the form of a solution as occasion demands, and there is no particular limitation.

[0164] In preparing the solution of the chemical treatment agent, the solvent used at this time is not particularly limited as long as it can dissolve the chemical treatment agent and does not destroy (e.g., dissolve) the existing carrier structure of the magnesium compound or the magnesium-aluminum carrier.

[0165] Specific examples of the alkanes include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, and the like, and among them, hexane is preferred. 5-12 alkanes, C 5-12 cycloalkanes, halogenated C 5-12 alkanes, and halogenated C 5-12 cycloalkanes, and the like, such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, chlorinated pentane, chlorinated hexane, chlorinated heptane, chlorinated octane, chlorinated nonane, chlorinated decane, chlorinated undecane, chlorinated dodecane, and chlorinated cyclohexane, and the like, and among them, pentane, hexane, decane, and cyclohexane are preferred, and hexane is most preferred.

[0166] These solvents can be used singly or in combination in any ratio.

[0167] In addition, the concentration of the chemical treatment agent in the solution thereof is not particularly limited and can be appropriately selected as needed as long as it can achieve the chemical treatment reaction with the predetermined amount of the chemical treatment agent. As described above, if the chemical treatment agent is in a liquid state, the chemical treatment agent can be directly used for the treatment, but it can also be used after being adjusted into a solution of the chemical treatment agent.

[0168] In general, the molar concentration of the chemical treatment agent in the solution thereof is generally set to 0.01 to 1.0 mol / L, but is not limited thereto.

[0169] As the method of performing the treatment, the above-described alkane solvent of the present application is added to the magnesium-aluminum carrier, and then, optionally, the non-metallocene ligand and the chemical treatment agent are added under stirring. The order of addition of the non-metallocene ligand and the chemical treatment agent is not particularly limited, and the non-metallocene ligand can be added first and then the chemical treatment agent can be added, or the chemical treatment agent can be added first and then the non-metallocene ligand can be added, or the non-metallocene ligand and the chemical treatment agent can be added at the same time. Preferably, the non-metallocene ligand is added first and then the chemical treatment agent is added.

[0170] In one embodiment of the present application, as the method of treatment, first the alkane solvent is added to the magnesium-aluminum support, then the non-metallocene ligand (which is optionally in solution form) is added in a metered manner under stirring, and further, when the chemical treatment agent used is in solid state (such as zirconium tetrachloride), it is preferred to first prepare a solution of the chemical treatment agent, then add (preferably dropwise) a predetermined amount of the chemical treatment agent to the solution of the magnesium-aluminum support and non-metallocene ligand to be treated; when the chemical treatment agent used (such as titanium tetrachloride) is in liquid state, a predetermined amount of the chemical treatment agent can be added (preferably dropwise) directly (but also after preparation in solution) to the solution of the magnesium-aluminum support and non-metallocene ligand to be treated.

[0171] In one embodiment of the present application, the treatment reaction is allowed to proceed (with the aid of stirring, if necessary) at a reaction temperature of -40 to 10°C (preferably -20 to 0°C) for 0.5 to 24 h, preferably 1 to 8 h, more preferably 2 to 6 h, and then, if necessary, filtration, optional washing and optional drying are carried out.

[0172] According to the present application, the filtration, washing and drying can be carried out using conventional methods, wherein the washing solvent can be the same as used for dissolving the chemical treatment agent or can be different. The washing is generally carried out 1 to 8 times, preferably 2 to 6 times, most preferably 2 to 4 times. The drying can be carried out, for example, by drying the magnesium support in situ loaded non-metallocene catalyst under vacuum at an absolute pressure of 2 to 100 mBar, preferably 5 to 50 mBar, for 2 to 30 h, preferably 4 to 12 h, thereby obtaining the dried magnesium support in situ loaded non-metallocene catalyst.

[0173] According to the present application, the molar ratio of the magnesium compound to the non-metallocene ligand, based on the Mg element, is 1 : 0.01 to 0.20, preferably 1 : 0.03 to 0.15.

[0174] According to the present application, the chemical treatment agent is used in such an amount that the molar ratio of the magnesium compound to the chemical treatment agent, based on the Mg element to the IVB group metal (such as Ti) element, is 1 : 1 to 20, preferably 1 : 2 to 10.

[0175] It is known to the person skilled in the art that all of the aforementioned method steps are preferably carried out under substantially water- and oxygen-free conditions. Substantially water- and oxygen-free means here that the water and oxygen content of the system is continuously less than 10 ppm. Furthermore, the supported non-metallocene catalyst of the present application, after preparation, generally needs to be stored under closed conditions at slightly positive pressure until use.

[0176] In one embodiment, the present application also relates to a magnesium carrier in-situ supported non-metallocene catalyst (sometimes also referred to as supported non-metallocene olefin polymerization catalyst) manufactured by the method for manufacturing a magnesium carrier in-situ supported non-metallocene catalyst of the preceding embodiment.

[0177] In a further embodiment, the present application relates to a process for olefin homo- or co-polymerization, wherein the olefin is homo- or co-polymerized in the presence of the supported non-metallocene catalyst of the present application as a catalyst for olefin polymerization.

[0178] As for the process for olefin homo- or co-polymerization according to the present application, other unspecified matters (such as polymerization reactor, amount of olefin, method of adding catalyst and olefin, etc.) other than those specifically indicated below can be directly applied to those conventionally known in the art and are not particularly limited, and the description thereof is omitted herein.

[0179] In one embodiment, the process for homo- or co-polymerization according to the present application, the magnesium carrier in-situ supported non-metallocene catalyst of the present application is used as a main catalyst, and one or more selected from aluminoxane, alkylaluminum, halogenated alkylaluminum, boron fluoride alkane, alkyl boron and alkyl boron ammonium salt is used as a cocatalyst, and the olefin is homo- or co-polymerized.

[0180] The method of adding the main catalyst and the cocatalyst to the polymerization system can be to add the main catalyst first and then add the cocatalyst, or to add the cocatalyst first and then add the main catalyst, or to mix both first and then add them together, or to add them simultaneously respectively. When the main catalyst and the cocatalyst are added respectively, they can be added sequentially in the same feeding line or sequentially in multiple feeding lines, and when they are added simultaneously respectively, multiple feeding lines should be selected. For continuous polymerization, multiple feeding lines are preferred for simultaneous continuous addition, and for batch polymerization, it is preferred to mix both first and then add them together in the same feeding line, or to add the cocatalyst first and then add the main catalyst in the same feeding line.

[0181] According to the present application, the reaction method for the process for olefin homo- or co-polymerization is not particularly limited and those conventionally known in the art can be used, such as slurry method, emulsion method, solution method, bulk method and gas phase method, among which slurry method and gas phase method are preferred.

[0182] According to the present application, as the olefin, C2~C 10 Monolefins, diolefins, cyclic olefins and other ethylenically unsaturated compounds.

[0183] Specifically, as the C2~C 10monolefins such as ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-undecene, 1-dodecene, and styrene; as the cyclic olefins, 1-cyclopentene and norbornene, and the like; as the diolefins, 1,4-butadiene, 2,5-pentadiene, 1,6-hexadiene, norbornadiene, and 1,7-octadiene, and the like; and as the other ethylenically unsaturated compounds, vinyl acetate and (meth)acrylate, and the like. Among them, homopolymerization of ethylene, or copolymerization of ethylene with propylene, 1-butene, or 1-hexene is preferred.

[0184] According to the present application, homopolymerization means polymerization of only one of the olefins, and copolymerization means polymerization between two or more of the olefins.

[0185] According to the present application, the cocatalyst is selected from the group consisting of aluminoxane, alkylaluminum, halogenated alkylaluminum, boron fluoride alkane, alkylboron, and alkylboron ammonium salt, among which aluminoxane and alkylaluminum are preferred.

[0186] As the aluminoxane, linear aluminoxane represented by the following general formula (III-1): (R)(R)Al-(Al(R)-O) n -O-Al(R)(R), and cyclic aluminoxane represented by the following general formula (III-2): -(Al(R)-O- n+2

[0187]

[0188] In the aforementioned general formulae, the groups R are the same as or different from each other (preferably the same), and each is independently selected from the group consisting of C1-C8 alkyl, preferably methyl, ethyl, and isobutyl, most preferably methyl; and n is an arbitrary integer in the range of 1 to 50, preferably an arbitrary integer in the range of 10 to 30.

[0189] As the aluminoxane, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and n-butylaluminoxane are preferred, methylaluminoxane and isobutylaluminoxane are further preferred, and methylaluminoxane is most preferred.

[0190] These aluminoxanes can be used singly or in combination of two or more in any ratio.

[0191] As the alkylaluminum, the same as the compound represented by the aforementioned general formula (I) of alkylaluminum, such as trimethylaluminum (Al(CH3)3), triethylaluminum (Al(CH3CH2)3), tripropylaluminum (Al(C3H7)3), triisobutylaluminum (Al(i-C4H9)3), tri-n-butylaluminum (Al(C4H9)3), triisopentylaluminum (Al(i-C5H 11 ​)3), tri-n-pentylaluminum (Al(C5H 11 )3), trihexylaluminum (Al(C6H 13 )3), triisohexylaluminum (Al(i-C6H 13 )3), diethylmethylaluminum (Al(CH3)(CH3CH2)2), and dimethylethylaluminum (Al(CH3CH2)(CH3)2), and the like, of which trimethylaluminum, triethylaluminum, tripropylaluminum, and triisobutylaluminum are preferred, triethylaluminum and triisobutylaluminum are further preferred, and triethylaluminum is most preferred.

[0192] These alkylaluminums can be used singly or in combination of a plurality of kinds in any ratio.

[0193] As the halogenated alkylaluminum, the boron fluoride alkyl, the alkylboron, and the alkylammonium boron salt, those conventionally used in the art can be used directly without particular limitation.

[0194] Further, according to the present application, the cocatalyst can be used singly or a plurality of the aforementioned cocatalysts can be used in combination as needed in any ratio without particular limitation.

[0195] According to the present application, depending on the reaction mode of the olefin homopolymerization / copolymerization method, sometimes a polymerization solvent needs to be used.

[0196] As the polymerization solvent, those conventionally used in the art when olefin homopolymerization / copolymerization is performed can be used without particular limitation.

[0197] As the polymerization solvent, for example, C 4-10 alkanes (such as butane, pentane, hexane, heptane, octane, nonane, or decane, and the like), halogenated C 1-10 alkanes (such as dichloromethane), aromatic hydrocarbon-based solvents (such as toluene and xylene), ether-based solvents (such as diethyl ether or tetrahydrofuran), ester-based solvents (such as ethyl acetate), and ketone-based solvents (such as acetone), and the like. Of these, hexane is preferably used as the polymerization solvent.

[0198] These polymerization solvents can be used singly or in combination of a plurality of kinds in any ratio.

[0199] According to the present application, the polymerization reaction pressure of the olefin homopolymerization / copolymerization method is generally 0.1 to 10 MPa, preferably 0.1 to 4 MPa, and more preferably 1 to 3 MPa, but is not always limited thereto. According to the present application, the polymerization reaction temperature is generally -40°C to 200°C, preferably 10°C to 100°C, and more preferably 40°C to 90°C, but is not always limited thereto.

[0200] Further, according to the present application, the olefin homopolymerization / copolymerization method can be carried out in the presence of hydrogen or in the absence of hydrogen. In the presence of hydrogen, the partial pressure of hydrogen can be 0.01% to 99% of the polymerization pressure, preferably 0.01% to 50%, but is not always limited thereto.

[0201] According to the present application, the molar ratio of the cocatalyst calculated as aluminum or boron to the supported non-metallocene catalyst calculated as Group IVB metal in carrying out the olefin homopolymerization / copolymerization method is generally 1:1 to 1000, preferably 1:1 to 500, more preferably 1:10 to 500, but is not always limited thereto.

[0202] Embodiments

[0203] The present application is further illustrated in detail by the following examples, but the present application is not limited to these examples.

[0204] The polymer bulk density (unit: g / cm3) is measured according to Chinese National Standard GB 1636-79. 3 ) is measured according to Chinese National Standard GB 1636-79.

[0205] The content of Group IVB metal (e.g., Ti) and Mg element in the supported non-metallocene catalyst is measured by ICP-AES method, and the content of non-metallocene ligand is measured by elemental analysis method.

[0206] The polymerization activity of the catalyst is calculated as follows: after the polymerization reaction is completed, the polymerization product in the reactor is filtered and dried, and then the mass of the polymerization product is weighed, and the polymerization activity of the catalyst (unit: kg polymer / g catalyst or kg polymer / g Cat) is represented by the ratio of the mass of the polymerization product to the mass of the used supported non-metallocene catalyst.

[0207] The viscosity average molecular weight of the polymer is calculated as follows: the intrinsic viscosity of the polymer is measured according to standard ASTM D4020-00 by high temperature dilution type Ubbelohde viscometer method (capillary inner diameter is 0.44 mm, constant temperature bath medium is 300# silicone oil, dilution solvent is decalin, and the measurement temperature is 135°C), and then the viscosity average molecular weight Mv of the polymer is calculated according to the following formula.

[0208] Mv = 5.37 x 10 4 x [η] 1.37

[0209] wherein η is the intrinsic viscosity.

[0210] The alcohol content in the carrier is determined as follows: quantitative analysis is performed by capillary gas chromatography using an Agilent 6890N gas chromatograph equipped with an automatic sampler and a hydrogen flame ionization detector (FID); the chromatographic column is DB-1 (30 m x 0.32 mm x 0.25 μm); the gas chromatography operating conditions are as follows: temperature: vaporization chamber 250°C, column temperature 60°C, detector 250°C; carrier gas is high-purity nitrogen; carrier gas flow rate is 1.4 ml / min; split ratio is 70:1; sample size is 0.2 ml; the reagent used for testing is chromatographically pure ethanol or n-butanol; ethanol is used to determine the ethanol content, n-butanol is used to determine the n-butanol content, and either ethanol or n-butanol can be used to determine the content of other alcohols; the relative retention time of ethanol is 2.426 min and that of n-butanol is 3.151 min. Ten different concentrations of the alcohol to be tested are accurately prepared in the reagent alcohol to serve as standards, and the calibration factor of each component is calculated under the gas chromatography conditions using the area normalization method to produce a graph of alcohol concentration index versus actual concentration. 1.00 g of the carrier is accurately weighed, 10 ml of the alcohol reagent is added, and the mixture is stirred at room temperature for 20 min, after which it is filtered; the filtrate is used as is. Under the gas chromatography conditions, the quantitative filtrate is automatically programmed into the automatic sampler for sampling and testing, and the alcohol concentration index of the filtrate is calculated by dividing the peak area of the alcohol to be tested by the total area; the actual alcohol concentration is obtained by substituting the index into the graph, and the alcohol content in the carrier is obtained after final conversion.

[0211] The polymer particle size distribution and fine powder content are determined by a Microtrac S3500 laser particle size analyzer, and the particle size measurement range is 0.01-10000 μm; the fine powder content is the volume ratio of the polymer having a particle size of less than 75 μm to the total polymer volume.

[0212] Example 1

[0213] 4.76 g of the magnesium compound is weighed into an alcohol, and the mixture is heated to 60°C under stirring until it is dissolved; then, a dilution solvent is added, and the mixture is stirred until it is uniform; then, the temperature is raised to 80°C, and the mixture is dried under a vacuum of 10 mBar for 2 h to obtain a magnesium carrier, wherein the alcohol content is 1.66 wt%.

[0214] 50 ml of a hexane solvent is measured and added to the magnesium carrier, and then alkyl aluminum is added dropwise under stirring at room temperature for 15 min; then, the temperature is raised to room temperature, and the mixture is reacted for 0.5 h; then, the temperature is raised to 40°C, and the mixture is reacted for 0.5 h; then, the temperature is raised to 60°C, and the mixture is reacted for 0.5 h; finally, the temperature is raised to 80°C, and the mixture is reacted for 1 h, wherein the temperature raising rate is 20°C / h. After the stirring and heating are stopped, the mixture is allowed to stand and settle, and then the obtained mixture is filtered and washed with 100 ml of hexane three times to obtain a magnesium-aluminum carrier.

[0215] To the magnesium-aluminum carrier, 50 ml of hexane was added, the non-metallocene ligand was added, the chemical treatment agent was added dropwise at -20°C for 15 minutes and stirred, after reaction at -20°C for 4 hours, filtered at normal temperature, washed with 100 ml of hexane for 3 times, and finally dried at normal temperature and under absolute pressure of 10 mBar for 6 hours to obtain the supported non-metallocene catalyst.

[0216] The magnesium compound is anhydrous magnesium chloride (MgCl2), the non-metallocene ligand is a compound with the structural formula The alcohol is anhydrous ethanol, the dilution solvent is decane, the alkyl aluminum is triethyl aluminum, and the chemical treatment agent is titanium tetrachloride (TiCl4).

[0217] The molar ratio of the magnesium compound to the alcohol calculated based on the Mg element is 1:17.1, the molar ratio of the magnesium compound to the non-metallocene ligand calculated based on the Mg element is 1:0.05, the ratio of the magnesium compound to the dilution solvent is 1 mol:2 L, the molar ratio of the magnesium compound to the triethyl aluminum calculated based on the Al element is 1:2, and the molar ratio of the magnesium compound to the chemical treatment agent titanium tetrachloride calculated based on the Ti element is 1:7.2.

[0218] The catalyst is recorded as CAT-1.

[0219] Example 2

[0220] The same as Example 1 basically, but with the following changes:

[0221] The non-metallocene ligand is a compound with the structural formula The magnesium compound is changed to n-butyl magnesium, the alcohol is anhydrous butanol, the dilution solvent is heptane, and the alkyl aluminum is triisobutyl aluminum. The alcohol content in the magnesium carrier is 1.42 wt%.

[0222] The molar ratio of the magnesium compound to the alcohol calculated based on the Mg element is 1:28.4, the molar ratio of the magnesium compound to the non-metallocene ligand calculated based on the Mg element is 1:0.075, the ratio of the magnesium compound to the dilution solvent is 1 mol:3 L, the molar ratio of the magnesium compound to the alkyl aluminum calculated based on the Al element is 1:3, and the molar ratio of the magnesium compound to the chemical treatment agent titanium tetrachloride calculated based on the Ti element is 1:4.

[0223] The catalyst is recorded as CAT-2.

[0224] Example 3

[0225] The same as Example 1 basically, but with the following changes:

[0226] The magnesium compound is anhydrous ethoxymagnesium (Mg(OC2H5)2), and the non-metallocene ligand is a compound with the structural formula The reducing compound is alcohol, the diluting solvent is cyclohexane, the alkyl aluminum is tri-n-hexyl aluminum (Al(C6H 13 )3), and the chemical treatment agent is zirconium tetrachloride (ZrCl4). The alcohol content in the magnesium carrier is 1.33 wt%.

[0227] The molar ratio of the magnesium compound to the alcohol is 1:22.6 in terms of Mg element; the molar ratio of the magnesium compound to the non-metallocene ligand is 1:0.12 in terms of Mg element; the ratio of the magnesium compound to the diluting solvent is 1 mol:1 L; the molar ratio of the magnesium compound to the alkyl aluminum in terms of Mg element to Al element is 1:1; and the molar ratio of the magnesium compound to the chemical treatment agent, zirconium tetrachloride, in terms of Mg element to Zr element is 1:9.5.

[0228] The catalyst is recorded as CAT-3.

[0229] Example 4

[0230] The example is basically the same as Example 1, but with the following changes:

[0231] The diluting solvent is changed to toluene.

[0232] The molar ratio of the magnesium compound to the alcohol is 1:25.7 in terms of Mg element; the ratio of the magnesium compound to the diluting solvent is 1 mol:1.5 L; the chemical treatment agent is added dropwise at -10°C and reacted for 4 h at -10°C; the molar ratio of the magnesium compound to the chemical treatment agent, titanium tetrachloride, in terms of Mg element to Ti element is 1:6; the molar ratio of the magnesium compound to the non-metallocene ligand is 1:0.10; and the alcohol content in the magnesium carrier is 1.76 wt%.

[0233] The catalyst is recorded as CAT-4.

[0234] Example 5

[0235] The example is basically the same as Example 2, but with the following changes:

[0236] The diluting solvent is changed to ethylbenzene, and the non-metallocene ligand is a compound with the structural formula .

[0237] The molar ratio of the magnesium compound to the alcohol is 1:10.26 in terms of Mg element; the ratio of the magnesium compound to the diluting solvent is 1 mol:2.5 L; the molar ratio of the magnesium compound to the chemical treatment agent, titanium tetrachloride, in terms of Mg element to Ti element is 1:4; the molar ratio of the magnesium compound to the non-metallocene ligand is 1:0.075 in terms of Mg element; and the alcohol content in the magnesium carrier is 1.21 wt%.

[0238] The catalyst is recorded as CAT-5.

[0239] Example 6

[0240] The same as Example 3, but with the following changes:

[0241] The dilution solvent was changed to xylene, and the non-metallocene ligand was changed to a compound having the structural formula .

[0242] The molar ratio of the magnesium compound to the alcohol was 1:29.07 in terms of Mg element, the ratio of the magnesium compound to the dilution solvent was 1 mol:3 L, the molar ratio of the magnesium compound to the chemical treatment agent zirconium tetrachloride in terms of Zr element was 1:15, and the molar ratio of the magnesium compound to the non-metallocene ligand in terms of Mg element was 1:0.15; the alcohol content in the magnesium carrier was 2.28 wt%.

[0243] This catalyst is denoted as CAT-6.

[0244] Comparative Example 1-1

[0245] The same as Example 1, but with the following changes:

[0246] The magnesium carrier was changed to one obtained by drying under a vacuum at an absolute pressure of 5 mBar for 10 h, in which the alcohol content was 0.60 wt%.

[0247] This catalyst is denoted as CAT-1-A.

[0248] Comparative Example 1-2

[0249] The same as Example 1, but with the following changes:

[0250] The magnesium carrier was changed to one obtained by drying under a vacuum at an absolute pressure of 10 mBar for 1 h, in which the alcohol content was 4.5 wt%.

[0251] This catalyst is denoted as CAT-1-B.

[0252] Comparative Example 1-3

[0253] The same as Example 1, but with the following changes:

[0254] The chemical treatment agent was added dropwise to a mixture containing the non-metallocene ligand, the magnesium-aluminum carrier, and hexane at 25°C, and the reaction was performed at 25°C for 4 h.

[0255] This catalyst is denoted as CAT-1-C.

[0256] Example 7 (Application Example)

[0257] The supported non-metallocene catalyst CAT-1-6, CAT-1-A-C and co-catalyst were weighed respectively and subjected to ethylene homopolymerization, copolymerization and preparation of ultra-high molecular weight polyethylene under the following conditions according to the following methods.

[0258] The homopolymerization was carried out in a 5L polymerization autoclave, slurry polymerization process, 2.5L hexane solvent, total polymerization pressure 0.8MPa, polymerization temperature 85℃, hydrogen partial pressure 0.2MPa, reaction time 2h. First, 2.5L hexane was added to the polymerization autoclave, and stirring was started, then 20mg of the supported non-metallocene catalyst and the co-catalyst mixture were added, and hydrogen was added to 0.2MPa, and finally ethylene was continuously introduced to keep the total polymerization pressure constant at 0.8MPa. After the reaction was completed, the gas in the autoclave was vented, the polymer in the autoclave was discharged, and the mass was weighed after drying. The specific conditions of the polymerization reaction and the polymerization evaluation results are shown in Table 1.

[0259] The copolymerization was carried out in a 5L polymerization autoclave, slurry polymerization process, 2.5L hexane solvent, total polymerization pressure 0.8MPa, polymerization temperature 85℃, hydrogen partial pressure 0.2MPa, reaction time 2h. First, 2.5L hexane was added to the polymerization autoclave, and stirring was started, then 20mg of the supported non-metallocene catalyst and the co-catalyst mixture were added, 50g of hexene-1 comonomer was added at one time, hydrogen was added to 0.2MPa, and finally ethylene was continuously introduced to keep the total polymerization pressure constant at 0.8MPa. After the reaction was completed, the gas in the autoclave was vented, the polymer in the autoclave was discharged, and the mass was weighed after drying. The specific conditions of the polymerization reaction and the polymerization evaluation results are shown in Table 1.

[0260] The preparation of ultra-high molecular weight polyethylene was carried out in a 5L polymerization autoclave, slurry polymerization process, 2.5L hexane solvent, total polymerization pressure 0.5MPa, polymerization temperature 70℃, reaction time 6h. First, 2.5L hexane was added to the polymerization autoclave, and stirring was started, then 20mg of the supported non-metallocene catalyst and the co-catalyst mixture were added, the molar ratio of the co-catalyst to the active metal of the catalyst was 100, and finally ethylene was continuously introduced to keep the total polymerization pressure constant at 0.5MPa. After the reaction was completed, the gas in the autoclave was vented, the polymer in the autoclave was discharged, and the mass was weighed after drying. The specific conditions of the polymerization reaction and the polymerization evaluation results are shown in Table 2.

[0261] Table 1. Effectiveness of magnesium carrier in-situ supported non-metallocene catalyst for olefin polymerization

[0262]

[0263] Table 2. Effectiveness of magnesium carrier in-situ supported non-metallocene catalyst for preparation of ultra-high molecular weight polyethylene polymerization

[0264]

[0265] The comparison of the effects of No.1 and No.3 in Table 1 shows that the copolymerization effect of the catalyst is remarkable, i.e. the copolymerization activity of the catalyst is higher than the homopolymerization activity, and the copolymerization reaction can improve the bulk density of the polymer, i.e. the particle morphology of the polymer is improved.

[0266] The comparison of the effects of No.1 and No.2 in Table 1 shows that the polymerization performance obtained under the conditions of the molar ratio of the cocatalyst to the active metal of the catalyst of 40 and 100 is equivalent, thus indicating that the catalyst provided by the present application requires less cocatalyst when used for olefin polymerization.

[0267] The comparison of the effects of No.1 and No.3 in Table 1 shows that the copolymerization effect of the catalyst is remarkable, i.e. the copolymerization activity of the catalyst is higher than the homopolymerization activity, and the copolymerization reaction can improve the bulk density of the polymer, i.e. the particle morphology of the polymer is improved. Figure 1 and Figure 2 It can be seen that the polymer obtained by using the in-situ supported non-metallocene catalyst provided by the present application has a fine average particle size and uniform distribution.

[0268] The comparison of No.1 and No.11, No.12 in Table 1, and No.1 and No.7, No.8 in Table 2 shows that too low or too high alcohol content in the magnesium carrier can result in reduced polymerization activity and bulk density of the polymer, and increased content of fine powder; when preparing ultra-high molecular weight polyethylene, the polymerization activity, bulk density of the polymer, and viscosity average molecular weight of the polymer are all reduced.

[0269] Although the specific embodiments of the present application have been described in detail above with reference to the embodiments, it should be pointed out that the protection scope of the present application is not limited by these specific embodiments, but is determined by the claims. Those skilled in the art can make appropriate changes to these embodiments without departing from the technical idea and the main points of the present application, and these changed embodiments are obviously included in the protection scope of the present application.

Claims

1. A method for preparing a magnesium carrier in-situ supported non-metallocene catalyst, comprising the steps of: a step of dissolving a magnesium compound in an alcohol, and then adding a dilution solvent, mixing and drying to obtain a magnesium carrier, wherein the content of the alcohol in the magnesium carrier is 1.2-2.5 wt% relative to the weight of the magnesium carrier; a step of adding an alkyl aluminum to the magnesium carrier for reaction, and filtering to obtain a magnesium aluminum carrier; a step of treating the magnesium aluminum carrier with a non-metallocene ligand and a chemical treatment agent selected from a Group IVB metal compound at -40-10°C to obtain the magnesium carrier in-situ supported non-metallocene catalyst, wherein the non-metallocene ligand is selected from one or more of the compounds having the following chemical structure formula: and the chemical treatment agent of the Group IVB metal compound is selected from one or more of a Group IVB metal halide, a Group IVB metal alkyl compound, a Group IVB metal alkoxyl compound, a Group IVB metal alkyl halide and a Group IVB metal alkoxyl halide.

2. The method according to claim 1, wherein the magnesium compound is selected from one or more of a magnesium halide, an alkoxyl magnesium halide, an alkoxyl magnesium, an alkyl magnesium, an alkyl magnesium halide and an alkyl alkoxyl magnesium.

3. The method according to claim 1 or 2, wherein the dilution solvent is selected from one or more of a paraffin hydrocarbon, a cycloparaffin hydrocarbon, a halogenated paraffin hydrocarbon, a halogenated cycloparaffin hydrocarbon and an aromatic hydrocarbon.

4. The method according to claim 1 or 2, wherein the alkyl aluminum is selected from one or more of trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, triisopentyl aluminum, tri-n-pentyl aluminum, tri-n-hexyl aluminum, triisohexyl aluminum, diethyl methyl aluminum and dimethyl ethyl aluminum.

5. The method according to claim 1 or 2, wherein the content of the alcohol in the magnesium carrier is 1.5-2.0 wt% relative to the weight of the magnesium carrier; and / or the step of treating the magnesium aluminum carrier with a chemical treatment agent selected from a Group IVB metal compound at -20-0°C to obtain the magnesium carrier supported non-metallocene catalyst; and / or the magnesium compound is selected from one or more of a magnesium chloride, an ethoxyl magnesium and a n-butyl magnesium; and / or the alcohol is selected from one or more of an ethanol, a propanol and a butanol; and / or the dilution solvent is selected from one or more of a hexane, a heptane, a decane, a cyclohexane, a toluene, an ethyl benzene and a dimethyl benzene; and / or the alkyl aluminum is selected from one or more of trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum and tri-n-hexyl aluminum.

6. The method according to claim 1 or 2, wherein the molar ratio of the magnesium compound to the non-metallocene ligand is 1:0.01-0.20 in terms of Mg element, the molar ratio of the magnesium compound to the alcohol is 1:10-50 in terms of Mg element, the ratio of the magnesium compound to the dilution solvent is 1 mol:0.5-4 L, the molar ratio of the magnesium compound in terms of Mg element to the alkyl aluminum in terms of Al element is 1:0.5-5, and the molar ratio of the magnesium compound in terms of Mg element to the chemical treatment agent in terms of Group IVB metal element is 1:1-20.

2. The production method according to claim 1, characterized by, 7. The method according to claim 1, wherein the magnesium carrier in-situ supported non-metallocene catalyst is used for preparing a polyolefin.

3. The production method according to claim 1 or 2, characterized by, The alcohol is selected from one or more of aliphatic, aromatic and alicyclic alcohols, wherein the alcohol is optionally substituted with a substituent selected from a halogen atom or a C 1-6 alkoxy group.

8. The method according to claim 1, wherein the magnesium carrier in-situ supported non-metallocene catalyst is used for preparing a polyolefin.

5. The production method according to claim 1 or 2, characterized by, ​ ​ ​ ​ ​ ​ ​ ​ 7. The production method according to claim 1 or 2, characterized by, ​ ​ ​ the chemical treatment agent of the Group IVB metal compound is selected from one or more of TiCl4, TiBr4, ZrCl4, ZrBr4, HfCl4, and HfBr4; and / or the molar ratio of the magnesium compound to the non-metallocene ligand is 1:0.03-0.15 in terms of Mg element, the molar ratio of the magnesium compound to the alcohol is 1:15-30 in terms of Mg element, the ratio of the magnesium compound to the dilution solvent is 1 mol:1-3 L, the molar ratio of the magnesium compound to the alkyl aluminum in terms of Mg element to Al element is 1:1-3, and the molar ratio of the magnesium compound to the chemical treatment agent in terms of Mg element to Group IVB metal element is 1:2-10.

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